International Journal of Applied Chemistry.

ISSN 0973-1792 Volume 13, Number 3 (2017) pp. 663-672

© Research India Publications
http://www.ripublication.com

A Concise Review on Surfactants and Its Significance

Nikunj Davea & Tejas Joshib

a
Department of Chemistry, Pacific University (PAHER), Udaipur, Rajasthan, India.
b
Department of Chemistry, UGC NON-SAP & DST-FIST Sponsored Department,
Maharaja Krishnakumarsinhji Bhavnagar University, Bhavnagar, India.

Abstract
Surface active agents constitute an interesting class of substances with unique
structural features. This review provides an introduction to the nature and
physical properties of surfactants, its trade name, types, characteristics and
their basic applications. Fundamental of critical micelle concentration (CMC),
cloud point, kraft point are mentioned. Surfactant size and shape are vital
characteristics and provide unique information during industrial formulation.
Surfactant properties play significant roles in industrial and consumer products
including detergents, paints, paper products, pharmaceuticals and cosmetics.
The last few years show an increased interest in work involving the
preparation and study of surfactants based on natural products.
Keywords: Surfactant, cmc, micelles, krafft points, cloud points

INTRODUCTION
The word surfactant is an abbreviation of the term Surface active agents having dual
characteristics of hydrophilicity and hydrophobicity and it itself suggests the surface
active nature of these classes of compounds and their tendency to adsorb at interfaces.
The polar portion exhibits a strong affinity or attraction towards polar solvents and it
is often called hydrophilic part or hydrophile. The apolar part is called hydrophobe or
lipophile having attraction towards oil [Figure 1]. [1-5]
664 Nikunj Dave & Tejas Joshi

Figure 1: Surfactant Molecule

Surfactants are also known as amphiphiles or tensides. The word amphiphile was
coined by Paul Winsor more than 50 years ago. It comes from two Greek roots.
Surfactant in French known as “tensioactif”, in German it is known by the name
“tenside” and in Spanish it is called “tensioactivo”. [6, 7]

Etymology
Interesting combination of English, Greek and Latin make sense to understand
about history of words, their origins, and how their form and meaning have changed
over time [Table 1]. [8]
Table 1: Etymology
English Greek Latin
oil lipo- oleo-
water hydro- aqua-
solvent lyo- solvo-
both amphi-
affinity -philic
lacking of -phobic
affinity
A Concise Review on Surfactants and Its Significance 665

Technical terms are formed by combinations of these words, such as:

 amphipathic = combining both natures (oil and water)
 amphiphilic = with affinity for both (oil and water)
 hydrophilic = with affinity for water
 lipophilic = with affinity for oil
 lyophilic = with affinity for the solvent
 lyophobic = lack of affinity for the solvent
 Categorization of surfactants

Surfactant can be classified into four broad categories: anionic, cationic, amphoteric
and nonionic. [Figure 2] [9-15]

Figure 2: Categorization of surfactants

Anionic surfactants give rise to a negatively charged surfactant ion upon dissolution in
water. This is the most widely used type of surfactant for laundering, dishwashing
liquids and shampoos because of its excellent cleaning properties. Most of the anionic
surfactants are carboxylate, sulfate and sulfonate ions. The most commonly used
anionic surfactants are alkyl sulphates, alkyl ethoxylate sulphates and soaps. Anionic
surfactants are relatively nontoxic. The straight chain is a saturated/unsaturated C12-C18
aliphatic group. The water solubility potential of the surfactant is determined by the
presence of double bonds in it. In solution, the head is negatively charged. The
surfactant is particularly good at keeping the dirt away from fabrics, and removing
residues of fabric softener from fabrics. Figure 3 represent the structure of anionic
surfactant, Sodium dodecyl sulfate.
666 Nikunj Dave & Tejas Joshi

Figure 3: Sodium dodecyl sulfate

Cationic surfactants In solution, the head is positively charged. They are good
emulsifying agents. These surfactants have also been found to be good bactericides and
some find use as topical antiseptics. Their germicidal properties make them especially
useful in bathroom and hand sanitizers. Cationic surfactants are attracted to negatively-
charged sites; they can bind to these sites and provide the fabric with a soft,
comfortable feel. Due to this reason, they are often used as fabric softeners. CTAB is
suitable example of cationic surfactant and is shown in Figure 4.

Figure 4: Cetyl trimethylammonium bromide (CTAB)

Zwitterionic surfactants also known as amphoteric surfactants have both cationic and
anionic centers attached to the same molecule. Zwitterionic surfactants are less
common than anionic, cationic and non ionic ones. These surfactants are very mild,
making them particularly suited for use in personal care and household cleaning
products. They are compatible with all other classes of surfactants and are soluble and
effective in the presence of high concentrations of electrolytes, acids and alkalis. These
surfactants may contain two charged groups of different sign. Whereas the positive
charge is almost always ammonium, the source of the negative charge may vary
(carboxylate, sulphate, sulphonate). These surfactants have excellent dermatological
properties. They are frequently used in shampoos and other cosmetic products, and also
in hand dishwashing liquids because of their high foaming properties. Typical example
of zwitterionic surfactant is alkyl betaine and lecithin which is shown in Figure 5.
A Concise Review on Surfactants and Its Significance 667

Figure 5: Alkyl betaine and lecithin

Nonionic surfactants
Surfactants that do not ionize in aqueous solution, due their hydrophilic group are of a
non-dissociable type, such as alcohol, phenol, ether, ester, or amide. These surfactants
do not have an electrical charge, which makes them resistant to water hardness
deactivation. They are excellent grease removers that are used in laundry products,
household cleaners and hand dishwashing liquids. A large proportion of these nonionic
surfactants are made hydrophilic by the presence of a polyethylene glycol chain,
obtained by the polycondensation of ethylene oxide. Non ionic surfactants are probably
the ones used most frequently in drug delivery applications. The nonionic surfactant
can be of polyol esters, polyoxyethylene esters, and poloxamers or pluronics.
Polyoxyethylene esters majorly include polyethylene glycol (PEGs). [Figure 6]. The
most commonly used nonionic surfactants are ethers of fatty Alcohol. Non-ionic
surfactants contribute to making the surfactant system less hardness sensitive.

Figure 6: Polyethylene glycol

 Physicochemical properties of surfactants

Fundamental property of surface active agents is that monomers in solutions tend to
form aggregates, called micelles or in other words, in aqueous solution, molecules
having both polar and non polar regions form aggregates called micelles. [16] In a
micelle, polar heads form an outer shell in contact with water, while non polar tails
are sequestered in the interior. Hence, the core of a micelle, being formed of long non
668 Nikunj Dave & Tejas Joshi

polar tails. Structure of micelle formation is shown in Figure 7. [17]

Figure 7: Micelle formation

The concentration at which micelles start to form is called critical micelle

concentration (CMC). It is an important phenomenon since surfactant molecules
behave very differently depending on whether they are present in micelles or as free
monomers. The micelles influence the solubility of organic hydrocarbons and oils in
aqueous solution and also influence the important property called viscosity. The size
of the micelle is measured by the aggregation number which is the number of
surfactant molecules associated with a micelle. Only surfactant monomers contribute
to surface and interfacial tension lowering. Wetting and foaming are governed by the
concentration of free monomers in solution. It was suggested by Adam [18] and
Hartley [19] that micelles are spherical in shape. In general the shape of the micelle is
dependent on the structure of the surfactant, typically the relative size of the head
group and tail group. Ionic surfactant form smaller micelles (aggregation number ~10-
70) than nonionic surfactants (Nagg  100). This is because the electrostatic repulsion
between ionic head-groups is greater than the steric repulsion between non-ionic head
A Concise Review on Surfactants and Its Significance 669

groups. The structure of a micelle could be of various shapes, spherical to rod- or

disc- like to lamellar. [20-25] In concentrated solution (much above the CMC); lamellar
micelles form, such that water molecules occupy the region between parallel sheets of
surfactant. [Figure 8]

Figure 8: Different shapes surfactant aggregates

Krafft point and Cloud Point

The solubility of micelle forming surfactants shows a strong increase above a certain
temperature, termed the Krafft point (KP). The Krafft point of ionic surfactant may be
defined as the temperature at which the solubility of surfactant becomes equal to its
CMC. Krafft point represents the temperature at which the alkyl chains melt resulting
in the dissolution of surfactant crystals into micelles and monomers as illustrated in
Figure 9.
670 Nikunj Dave & Tejas Joshi

Figure 9: Krafft point phenomena

The Krafft temperature is an essential parameter that must be known for a surfactant
before putting it into use. Since micelles form only at temperature above the Krafft
point, a surfactant is often required to possess a KP value lower than the temperature
at which it is used. Nonionic surfactants often do not exhibit Krafft points. Instead,
the solubility of nonionic surfactants decreases with increasing temperature and these
surfactants may begin to lose their surface active properties above a transition
temperature referred to as Cloud point.

CONCLUSIONS
Over the past two decades, new surfactant molecules have been appearing at a
relatively rapid pace. Scientific curiosity has also driven surfactant science research to
focus on surfactant molecules having interesting fabricated shapes and structures.
Fundamental knowledge of surfactant is very essential although surfactant science is
now very well established discipline and there is still room for new molecules
designed for specific purposes and new applications.

ACKNOWLEDGEMENT
Dr. Tejas P Joshi would like to thank Prof. N. C. Desai, Head, Dept. of Chemistry,
Maharaja Krishnakumarsinhji Bhavnagar University, Bhavnagar, for moral boosting.
A Concise Review on Surfactants and Its Significance 671

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672 Nikunj Dave & Tejas Joshi

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